Non-dusting detergent and bleaching composition



2,988,510 NON-DUSTING DETERGENT AND BLEACHING COMPOSITION Jay C. Harris, Thomas C. Tesdahl, and Richard M.

Anderson, Dayton, Ohio, assignors to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Filed June 1, 1956, Ser. No. 588,614 15 Claims. (Cl. 252-99) The present invention relates to detergent, bleaching, sterilizing, and disinfectant compositions which are nondusting and which contain N,N-dichloro-p-toluenesulfonamide; trichlorocyanuric acid, or other positive chlorine containing organic compounds as an active constituent.

An object of the invention is to provide non-dusting compositions of improved stability containing N,N-dichloro-p-toluenesulfonamide (also known as Dichloramine T) or trichlorocyanuric acid in combination with alkaline salts, particularly alkaline phosphates and silicates. It is, accordingly, an object of the invention to I provide dry compositions having reduced dusting characteristics, which are stable under ordinary conditions of storage and transportation and which, when dissolved in water, yield solutions suitable for washing, bleaching, sterilizing, and disinfecting.

A further object of the invention is to provide disinfecting detergents for use in cleaning containers, particularly metal vessels used in the bulk transport of milk, cream, and other milk products. An additional object of theinvention is to provide detergents having stabilized disinfecting properties for use in hospitals or similar institutions, as well as in hotels and restaurants for dishwashing and other purposes.

Other objects and advantages of the invention will be apparent to those skilled in the art as the description proceeds.

It has been found desirable in the formulation of detergent, bleaching, sterilizing, and disinfectant compositions, to provide therein an active source of chlorine. N,N- dichloro-p-toluenesulfonamide and trichlorocyanuric acid are preferred compounds in this relationship. However, certain other types of organic chlorine-containing com.- pounds are likewise of utility for this purpose. 7

The organic chlorine compounds contemplated in the present invention are those which contain a positive chlorine atom-i.e., a chlorine atom which has replaced an acidic hydrogen atom-with the result that the compound will hydrolyze in aqueous solution to yield hypochlorite ion.

One outstanding class of positive chlorine containing organic compounds are the N-chlorosulfonamides, and particularly the aryl sulfonamides. Examples of suitable compounds within this class are N,N-dichloro-ptoluenesulfonamide (also known as Dichloramine-T), N- chloro-p-toluenesulfonamide or the sodium salt thereof (known as Chlorarnine-T) p-(N,N-dichlorosulfonamide) benzoic acid, and the like.

Another outstanding class of positive chlorine containing compounds are those in which a chlorine atom has replaced the hydrogen of an activated imido group, and especially where the imido group has been activated by one or two acyl radicals connected directly to the nitrogen atom. Examples of suitable compounds of this type are the chlorine derivative of the keto form of cyanuric caid, N-chlorosuccinimide, N-chlorophthalimide, N,N-dichlorodimethylhydantoin, the chlorinated derivatives of melamine, ammeline, and ammelide, and numerous others which will be readily apparent to those skilled in the art.

Still another class of suitable positive chlorine connited States Patent 'ce 2,988,510 Patented June 13, 1961 taining organic compounds for use according to the present invention are compounds in which chlorine atoms have replaced an acidic hydroxyl hydrogen. Suitable examples of such compounds are the enol form of trichlorocyanuric acid, the dihypochlorite of dihydroxyoctachlorobiphenyl, the hypochlorite of trichlorophenol, etc.

In preparing formulations for dishwashing and other washing operations, such as laundering, bleaching, steiilizing, and disinfecting, the foregoing positive chlorine containing organic compounds may be used in combination with other ingredients, such as water-soluble, alkaline phosphate compounds and/ or certain water-soluble, silicate compounds, both of which are described more fully below.

The phostphate compounds are preferably chain polyphosphates. The polyphosphates are those phosphates containing more than one phosphorus atom per molecule, as distinguished from otrthophosphates which contain only one phosphorus atom per molecule. Chain polyphosphates are non-cyclic (and usually linear) phosphates, as distinguished from ring or cyclic phosphates, such as trimetaphosphate and tetrametaphosphate. Examples of the more common chain polyphosphates are tetrasodium pyrophosphate and sodium. tripolyphosphate, both of which can be obtained as essentially pure crystalline materials, and an amorphous polyphosphate known as sodium hexametaphosphate.

The amorphous polyphosphates, also known as glassy phosphates, are generally characterized either in terms of mole ratio of Na O to P 0 or in terms of average chain length of the polyphosphate molecules in the glassy phosphate. For example, a commercial sodium hexametaphosphate has a mole ratio of Na O to P 0 of' about 1.13, and an average chain length of about 15 phosphorus atoms. In general, any of the water-soluble glassy polyphosphates, which have mole ratios of Na O to P 0 ranging between about 5:3 and about 1:1 (corresponding to a range of average chain length from three to several thousands or higher) are suitable for use as the chain polyphosphate ingredient of the present invention.

While the immediately foregoing description has been in terms of sodium phosphates, it should be apparent that other alkali metal (particularly potassium) phosphates may be utilized in place of the corresponding sodium phosphates. It should also be pointed out that mixtures of two or more of the various chain polyphosphates described above can often be used to advantage in practicing the present invention.

A water-soluble silicate, such as sodium or potassium silicate is the other ingredient which may be utilized along with the above-described chlorine-containing compounds and chain polyphosphates in dry concentrates for aqueous wash solutions prepared according to this invention. As is well known, sodium silicates, for example, can vary quite widely in composition range from a mole ratio of Na O:SiO of 1:4 to the more alkaline silicates, such as the orthosilicate having a mole ratio of Na O:SiO ratio of 2:1. Mixtures of silicates having an overall molar ratio of Na O:SiO between about 1:4 and..2:l and preferably between about 123.5 and 1:1 can be utilized if desired.

In formulating and using the above mixtures of active chlorine compounds with phosphates and/ or silicates, dusting is a major problem. However, it has been found that the addition of conventional dedusting agents, such as mineral oil, and other unsubstituted hydrocarbons results in the rapid deterioration of the available chlorin content.

It has now been found that the employment of certain silicone compounds in the present alkaline active chlorine formulations reduces the dusting tendency while at the same time avoiding objectionable deterioration of the said chlorine-containing compound. The essential combination of the present invention comprises the said silicone with the active chlorine compounds. However, the invention also includes combinations of these essential the compositions of the present invention can be readily understood by reference to the following examples:

Example 1 components with phosphates and/or silicates as well as 5 A sterilizing dishwashmg composltlon s prepared other iugredieutu employing the following components which were mlxed in It has now been found that the preparation of the the y State: above detergent bleaching, sterilizing and disinfecting Percent compositions in dry form may be improved by the in- N.N-d1chlqr0-Pt 1uenesulfonamlde corporation therein of certain silicones to control dust- Sodium tllpollfBhosphate 50 ing. A preferred group are the methyl silicones, although Sodium metaslhcate 25 ethyl and phenyl silicones as well as ethylphenyl silicones soda ash 23 having both substituents, and also physical combinations The above formulation tested as a control i above may Similarly be employed- The meihyl ture relative to a similar formulation additionally consilicones which are employed in the present compositions mining 1% f a h l i i h i a viscosity f 3 have the general formula: centistokes at 100 F. It was found that the mixture CHs CHa CHa without the methyl silicone was very dusty, but that the l formulation containing the said methyl silicone could be I l I handled and dispensed in powder form without dusting or CH3 CH3 objectionable nasal irritation. in which x represents the degree of polymerization in- Example 2 fluencing the viscosity of the composition. The viscosity of the silicones employed in the present invention may g g gi f s gigggg; fi g i g? 5 T}; vary firomto 1500 centlstokes' The propomon of methyl silicone having viscosities of 0.58 1.7 and 13 the said silicone may vary over a range of from 0.05% e k F 1 It I f d th t to 10% by weight, a preferred range being from 0.1% centlsto 1 5 We .i g to 2.0% by weight of the overall composition. @9 of e foimu ate etergents p i is y The above-described silicones are advantageously forslhconefledusflnghagent i substalntlal ust mulated with an active chlorine-containing compound as cqnpanson to t e Collin-o g? :3 w 10 ac ed t e a dry, granular concentrate which overcomes the inherent slllcone"and consequent y duste dustiness of the chlorine compound. Such dry concen- Example 3 trates may be utilized for further formulating. The ultimate compositions are then adapted to be added to an g ggi ifig f g i g gg zfi gi g g gg g u fi 3 55 5: i g i g gi fifgg 253E222 3?;: :s ?g phenyl silicone having a viscosity of 8 centistokes at 100 The above discussed ingredients can be formulated into gu detergent was found to be substantlany free of dry, granular concentrates suitable for addition to an Exam 4 appropriate amount of Water to form aqueous solutions p having utility as dishwashing solutions, laundry bleaches, 40 A bleaeh for laundering, disinfecting deodofiziflg disinfecting or deodorizing solutions. Such dry concenwas P p y y blending the following ingredients trates may, in general, be prepared in the fol-lowing ranges g P as a yp example: of concentrations as broad ranges and preferred ranges Percent expressed in percent by Weight; Sodium tripolyphosphate i Sodium sulfate 69.8 Y Trichlorocyanuric i '10 351 53351 335 c ifiiigiliim General Methyl Silicone.- Component Formula The above samples were sub ected to an accelerated de- Bmad Broad gradation test at 120 F. in which 35 days of accelerated Ph h t degradation is equivalent to 8 to 18 months of normal f fgii 21:2: 33% igjgg 82% 18:28 8:?2 storage. The test determines the effect of the dedusting iodiumugate, etc 0-60 20450 11-75 20-60 o-75 agent upon the loss of available chlorine from the N,N- iti di il i 13 5 1?; 32- 3 dichloro-p-toluenesulfonamide or trichlorocyanuric acid. A control test was also made using an oily material, e.g., Nujol mineral oil. The table below shows the percentage In general the dry formulations should have sufiicient loss of positive chlorine after 20 days and 35 days of organic chlorine-containing compound to make the posistorage at 120 F., and also provides identification data tive chlorine content fall in the following ranges: With respect to the various dedusting stabilizers employed.

11)isl1vmsh- Bleaching Loss of Positive ng Com- Oomposi- General, Viscosity, Chlorine (percent) position, tion, perpercent Stabilizing Compound Oentistokes percent cent 100 F 20 Days 35 Days Broad range 0. 05-5 0. 05-43 0. 05-43 Preferred range 0. 1-2 2-5 0.1-5 Mineral oil 380 25 55 I '1 1 1 Meth lsilicone Additional ingredients such as soda ash (e.g:, 0-60%, y i 1% 1 and preferably 20-60% by weight), sodiu lf t t ylph uyl silicone 8 9 14 dium chloride, dyes, perfumes, etc. can also be incorporated into the dry mixture if desired. However, the com- 7 The above data indicate that an unsubstituted hydro posmfms must be kept free of any readily oxidizable or carbon, i.e., mineral oil is ineffective as adedusting a ent, chlorinatabie organic matter which would react with the since the 1 f available chlorine is very j h z Graeme chlollne-comalniflg Components of this invention trast thereto the various silicone compounds show very Further details relative to the techniques and procedures small lo f hl in d it th lon ed storage. at to be followed in carrying out the process and utilizing 7 5 high temperature.

The above formulation, when dissolved in water, provides an active bleaching composition useful for bleaching cloth by treatment with such aqueous solution. The dry mixture, when contacted with water, produces hypochlorite chlorine.

What is claimed is:

1. A dry granular composition which comprises an active organic chlorine-containing compound in combination with a silicone selected from the group consisting of methyl silicones, ethyl silicones, phenyl silicones, ethylphenyl silicones and combinations thereof the proportion of the said silicone being from 0.05% to by weight of the overall composition.

2. A dry granular composition which comprises an active organic chlorine-containing compound in combination with a methyl silicone, the proportions of the said silicone being from 0.05% to 10% by weight of the overall composition.

3. A dry granular composition which comprises an active organic chlorine-containing compound in combination with an ethylphenyl silicone, the proportion of the said silicone being from 0.05 to 10% by weight of the overall composition.

4. A dry granular composition which comprises an active organic chlorine-containing compound in combination with a silicone selected from the group consisting of methyl silicones, ethyl silicones, phenyl silicones, ethylphenyl silicones and combinations thereof, the said silicone having a viscosity of from 0.2 to 1,500 centistokes at 100 F., the proportion of the said silicone being from 0.05 to 10% by weight of the overall composition.

5. A dry granular composition which comprises an active organic chlorine-containing compound in combination with a methyl silicone, the said silicone having a viscosity of from 0.2 to 1,500 centistokes at 100 F., the proportion of the said silicone being from 0.05% to 10% by weight of the overall composition.

6. A dry granular composition which comprises an active organic chlorine-containing compound in combination with an ethylphenyl silicone, the said silicone having a viscosity of from 0.2 to 1,500 centistokes at 100 F., the proportion of the said silicone being from 0.05 to 10% by weight of the overall composition.

7. A dry granular composition which comprises N,N- dichloro-p-toluene sulfonamide in combination with a silicone selected from the group consisting of methyl silicones, ethyl silicones, phenyl silicones, ethylphenyl silicones and combinations thereof, the said silicone having a viscosity of 0.2 to 1,500 centistokes at 100 F., the proportion of the said silicone being from 0.05 to 10% by weight of the overall composition.

8. A dry granular composition which comprises N,N- dichloro-p-toluenesulfonamide in combination with a methyl silicone having a viscosity of 0.2 to 1,500 centistokes at 100 F., the proportion of the said silicone being from 0.05% to 10% by Weight of the overall composition.

9. A dry granular composition which comprises N,N- dichloro-p-toluenesulfonamide in combination with an ethylphenyl silicone having a viscosity of 0.2 to 1,500 centistokes at 100 F., the proportion of the said silicone being from 0.05% to 10% by weight of the overall composition.

10. A dry granular composition which comprises trichlorocyannric acid in combination with a silicone selected from the group consisting of methyl silicones, ethyl silicones, phenyl silicones, ethylphenyl silicones and com- 6 binations thereof, the said silicone having a viscosity of from 0.2 to 1,500 centistokes at F., the proportion of the said silicone being from 0.05 to 10% by weight of the overall composition.

11. A dry granular composition which comprises trichlorocyannric acid in combination with a methyl silicone having a viscosity of 0.2 to 1,500 centistokes at 100 F., the proportion of the said silicone being from 0.05% to 10% by weight of the overall composition.

12. A dry granular composition which comprises trichlorocyannric acid in combination with an ethylphenyl silicone having a viscosity of 0.2 to 1,500 centistokes at 100 F., the proportion of the said silicone being from 0.05 to 10% by weight of the overall composition.

13. A dry granular composition which comprises between about 25% and about 60% of sodium tripolyphosphate, between about 10% and 60% of sodium silicate, between about 20% and 60% of sodium sulfate, between about 0.05 and 10% of an active organic chlorine-containing compound and about 0.1% to 10% by Weight of a silicone selected from the group consitsing of methyl silicones, ethyl silicones, phenyl silicones, ethylphenyl silicones and combinations thereof, the said silicone having a viscosity of from 0.2 to 1,500 centistokes at 100 F.

14. A dry granular composition which comprises between about 10 and about 60 weight percent of sodium tripolyphosphate, between about 20% and about 60% of sodium sulfate, suficient trichlorocyannric acid to make the chlorine content of the said composition equal to be tween about 2 and about 5% of said composition, and about 0.05 to about 10% by weight of a methyl silicone having a viscosity of 0.2 to 1,500 centistokes at 100 F.

15. The method of inhibiting the decomposition of active organic chlorine-containing compounds which comprises contacting the same with a silicone selected from the group consisting of methyl silicones, ethyl silicones, phenyl silicones, ethylphenyl silicones and combinations thereof, the said silicone having a viscosity of from 0.2 to 1,500 centistokes at 100 F. the said silicone being employed in the proportions of from about 0.05% to about 10% by weight of the overall composition.

References Cited in the file of this patent UNITED STATES PATENTS 1,555,805 Kroeber Sept. 29, 1925 1,609,328 Taylor Dec. 7, 1926 1,892,548 Feibelmann Dec. 27, 1932 2,195,757 Robson et al. Apr. 2, 1940 2,423,450 Heald et al. July 8, 1947 2,578,270 Strain Dec. 11, 1951 2,598,436 Mohler et a1 May 27, 1952 2,604,469 Herrmann July 22, 1952 2,607,738 Hardy Aug. 19, 1952 2,647,892 Brie et al. Aug. 4, 1953 Jenkins Apr. 17, 1956 OTHER REFERENCES Chemistry of the Silicones, by Rochow, page 87, pub. by John Wiley, New York, 1946.

Dow Corning Silicone Notebook Ref. No. 2203, issued June 1952, pages 4, 5, 13, 17 and 18.

Morel: Science et Technologie, Rev. Gen. Caoutchouc, vol. 30, No. 7, 1953, pages 481-489.

Pfeifer et al.: India Rubber World, January 1954, pages 481-484, 488. 

13. A DRY GRANULAR COMPOSITION WHICH COMPRISES BETWEEN ABOUT 25% AND ABOUT 60% OF SODIUM TRIPOLYPHOSPHATE, BETWEEN ABOUT 10% AND 60% OF SODIUM SILICATE, BETWEEN ABOUT 20% AND 60% OF SODIUM SULFATE, BETWEEN ABOUT 0.05% AND 10% OF AN ACTIVE ORGANIC CHLORINE-CONTAINING COMPOUND AND ABOUT 0.1% TO 10% BY WEIGHT OF A SILICONE SELECTED FROM THE GROUP CONSISTING OF METHYL SILICONES, ETHYL SILICONES, PHENYL SILICONES, ETHYLPHENYL SILICONES AND COMBINATIONS THEREOF, THE SAID SILICONE HAVING A VISCOSITY OF FROM 0.2 TO 1,500 CENTISTOKES AT 100*F.
 15. THE METHOD OF INHIBITING THE DECOMPOSITION OF ACTIVE ORGANIC CHLORINE-CONTAINING COMPOUNDS WHICH COMPRISES CONTACTING THE SAME WITH A SILICONE SELECTED FROM THE GROUP CONSISTING OF METHYL SILICONES, ETHYL SILICONES, PHENYL SILICONES, ETHYLPHENYL SILICONES AND COMBINATIONS THEREOF, THE SAID SILICONE HAVING A VISCOSITY OF FROM 0.2 TO 1,500 CENTISTOKES AT 100*F. THE SAID SILICONE BEING EMPLOYED IN THE PROPORTIONS OF FROM ABOUT 0.05% TO ABOUT 10% BY WEIGHT OF THE OVERALL COMPOSITION. 